Composition containing glycidyl polyether of a polyhydric phenol, a methylol substituted 2-alkenyloxybenzene, and a polyvinyl acetal



United States Patent C) Harry W. Howard, South Orange, Cliilord V. Witteriwyler, Fanwood, and Otho L. Nikles, Jr., Metuchen,

J., assignors to Shell Development Company, Emeryville, Calif., a corporation of Delaware No Drawing. Original application April 14, 1952, Serial No. 282,274. Divided and this application May 24, 1954, Serial No. 432,028

8 Claims. (Cl. 26043) This invention relates to a new composition of matter capable of being cured with the aid of acidic curing agents to a resinous product which is particularly adapted This application is a division of copending application, Serial No. 282,274, filed April 14, 1952.

The composition of the invention comprises a mixture of (l) glycidyl polyether of a polyhydric phenol having a 1,2-epovy equivalency greater than 1.0, (2) a 2-alkenyloxybenzene having 1 to 3 methylol groups which are linked singly at the 2, 4 and 6 positions on the benzene ring, and (3) about 0.2% to 3% of a polyvinyl acetal resin. A particular embodiment of the invention is the composition comprising (1) glycidyl polyether of a dihydric phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 in admixture (less than 50% by weight) methylol groups which are linked 6 positions on the benzene ring, and (3) about 0.2% to 3% of a polyvinyl acetal resin. An especially suitable embodiment of the invention is the composition containing glycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane in uniform combination with a mixture of allyloxybenzenes having 1 to 3 methylol groups which are linked singly at the 2, 4 and 6 positions oxybenzene having 3 methylol groups linked to the henzene ring, and which composition also contains about 0.2% to 3% of a polyvinyl acetal 2 to 4 carbon atoms.

The glycidyl polyethers of polyhydric phenols are obtainable by reacting a polyhydric phenol with epichlorhydrin in basic medium at about 50 use of more than one mole of epichlorhydrin per equivalent of phenolic hydroxyl group of the phenol and a slight stoichiometric excess of base such as about 2% to 30% excess sodium or potassium hydroxide. The reaction is eifected by heating for several hours and the product is then separated from formed salt, excess base, and It is usually preferred to dihydric phenol in the inan average which is not necessarily zero or a whole number. Although the polyether is a substance primarily of the above formula, it may contain some material with one or both of the terminal glycidyl radicals in hydrated form,

of a dihydric phenol. It contains a single divalent aromatic hydrocarbon radical from the dihydric phenol and has two glycidyl radicals linked thereto by ethereal oxygen atoms. More generally, the polyether of dihydric phenols is of more complex character and contains two or more aromatic hydrocarbon radicals alternating with glyceryl groups in a chain which are linked to ether by intervening ethereal oxygen atoms.

The 1,2-epoxy equivalency of the glycidyl polyether refers to the number of 1,2-epoxy groups After cooling, the excess unreacted pyridinium chlorideis back-titrated with 0.1 N sodium hydroxide in methanol to the phenolphthalein end point. The epoxide value is calculated by considering one HCI as equivalent to one epoxide group. This method epoxide values discussed herein.

Any of the various polyhydric phenols is used in preparing the polyethers employed in the invention including mononuclear phenols such as resorcinol, catechol, hydroquinone, methyl resorcinol, etc.; or polynuclear phenols like 2,2-bis(4-hydroxyphenyl)propane which is termed bis-phenol herein for convenience 4 4'-dihydroxyhydroxyphenyl)ethane, 1,1bis(4 hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy- 2-methylphenyl)propane, 2,2 bis(4-hydroxy-2-tertiarybis(2-hydroxynaphthy1)penas well as more tion catalyst. Preparation of glycidyl polyether of novolac resin is described in Example 27 of German Patent No. 676,117.

Particularly preferred polyethers used in the invention are prepared from 2,2-bis(4-hydroxyphenyl)propane. They contain a chain of alternating glyceryl and 2,2-bis(4- polyethers of 2,2-bis(4-hydroxyphenyl)propane have a molecular weight of about 1200 to 4000 as is the case when n is about 3 to 13 in the above-described structural formula.

wherein n is an integer of the series 0, l, 2, 3 and R represents the divalent hydrocarbon radical of the dihydric phenol. While for any single molecule of the polyether n is an integer, the fact that the obtained polyether is a mixture of compounds causes the determined value for n, e. g. from molecular weight measurement, to be The glycidyl polyethers will be better understood from consideration of the following described preparations and the properties of the products. The parts are by weight.

POLYETHER A In a vessel fitted with an agitator, 228 parts (1 mole) of bis-phenol and 55 parts (1.37 moles) of sodium hydroxide as a aqueous solution are introduced and heated to about C. whereupon 113 parts (1.22 moles) of epichlorhydrin are added rapidly while agitating the mixture. The temperature of the mixture is then gradually increased and maintained at about C. for 80 minutes. The mixture separates into a two-phase system and the aqueous layer is drawn off from the taffylike product which forms. The latter is washed with hot water while molten until the wash water is neutral to litmus. The product is then drained and dried by heating to a final temperature of about C. The resulting glycidyl polyether of 2,2-bis( 4-hydroxyphenyl)- propane has a Durrans Mercury Method softening point of 98 C. and an epoxide value of 0.11 epoxy equivalents per 100 grams. The molecular weight measured ebullioscopically in ethylene dichloride is 1400. The 1,2- epoxy equivalency is 1.5. The product will be identified hereinafter as polyether A.

POLYETHER B Glycidyl polyethers of higher molecular weight are most easily prepared by heating together and reacting a lower polyether with additional dihydric phenol. Thus ture to about 200 C. The resulting glycidyl polyether has a Durrans softening point of 131 C., a molecular weight of 2900, an epoxide value of 0.05 epoxy equivalents per 100 grams, and a 1,2-epoxy equivalency of 1.5.

POLYETHER C This polyether is prepared as described for polyether B except that 100 parts of polyether A are mixed, heated and reacted with 7.75 parts of bis-phenol. The resulting product has a Durrans softening point of 146 C., a molecular weight of 3750, an epoxide value of 0.036 epoxy equivalents per 100 grams, and a 1,2-epoxy equivalency of 1.4.

The 2-alkenyloxy benzene containing 1 to 3 methylol groups as substituents on the benzene ring that is employed in admixture with a glycidyl polyether in the compositions of the invention include a variety of particular compounds. The 2-alkenyl radical in the compound has an olefinic double bond between the beta and gamma carbon atoms, the saturated alpha carbon atom being linked to the ether oxygen atom. Among typical Z-alkenyl radicals contained in the compounds are allyl, methallyl, crotyl, 2-pentenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, Z-hexenyl or like groups. If desired, the Z-alkenyl radical may contain one or more halogen substituents as is the case with 2-chloroal1yl, 3-chloroallyl, 2-bromoallyl, 2-chlor0-2-methylallyl, 2,3-dichloroallyl, and like groups. It is preferred to employ a compound containing three methylol groups linked to the benzene ring, but other compounds containing only one or two methylol groups linked singly at any one of the 2, 4 and 6 positions are also suitable. Although substantially pure compounds can be used in practicing the invention, it is more usual that a mixture of the Z-alkenyloxy compounds be contained in the composition. This is because production of the compounds, which is effected in known manner, normally gives a mixture which is equally suitable. The produced mixture normally contains a 2- alkenyloxybenzene having three methylol groups linked singly at the 2,4 and 6 positions on the benzene ring in admixture with a minor proportion of Z-alkenyloxybenzenes having one to two methylol groups linked singly at the 2, 4 and 6 positions of the benzene ring. Normally the 2-alkenyl radicals in the mixture of compounds are the same for each. Especially suitable compounds of the class, whether used singly or as mixtures, are those wherein the 2-alkenyl radical is the allyl group. Reference is made particularly to allyloxy-2,4,6-tri(hydroxymethylbenzene.

The inclusion of about 0.2% to 3%, preferably about 0.5% to 2% of a polyvinyl acetal resin is useful in com positions employed for surface coating purposes. Compositions containing the glycidyl polyether and the 2- alkenyloxybenzene compound which are applied as solutions to surfaces have some tendency to crawl which is formation of regions of different thickness of film. The presence of a polyvinyl acetal resin prevents this tendency. Although various polyvinyl acetal resins are suitable for overcoming the crawling of the films, it is preferred to employ polyvinyl acetal resins of saturated aldehydes (alkanals) of 2 to 4 carbon atoms, of which polyvinyl butyral resin has been found preferable.

The compositions of the invention are prepared by bringing the methylol-substituted 2-alkenyloxybenzene into uniform admixture with the glycidyl polyether and the polyvinyl acetal resin. Most of the methylol-substituted 2-alkenyloxybenzenes preferred for use are liquid at ordinary temperature of about 20 C. When the glycidyl polyether is also liquid at normal temperature, the compositions are easily prepared by stirring the two components together. The glycidyl polyethers, even in solid form, dissolve in the methylol-substituted 2-ailkenyloxy compounds and the compositions are thus obtainable by mixing and dissolving solid glycidyl polyether in the liquid second component. Application of heat to one or both components assists in obtaining homogeneous mixture thereof. One or both of the components are heated to fluidized temperature such as up to about C. and mixing is effected.

Since one of the principal uses of the composition is as a surface coating material in cured condition and application to a surface is usually effected with a solution of the composition, it is convenient to prepare the composition with use of mutual solvents. Various normally liquid organic compounds are suitable for this purpose including ketones such as methyl ethyl ketone, methyl isobutyl ketone, mesityl oxide, cyclohexanone, isophorone, etc.; ethers and ether-esters of glycols such as monomethyl, monoethyl and monobutyl ether of ethylene glycol, diethylene glycol, and propylene glycol and the corresponding acetates and propionates; halogenated hydrocarbons such as ethylene dichloride, trichloropropane, etc. Instead of using only active solvents, it is more customary to utilize a mixture of one or more active solvents with one or more diluents. For this purpose, aromatic hydrocarbons are suitable such as benzene, toluene, xylene, etc. Alcohols such as ethanol, butanol and methyl isobutyl carbinol are also useful constituents of the solvent mixture. In using solutions of the composition of the invention for surface coating purposes, solutions of suitable spraying or brushing viscosity are employed that contain about 20% to 60% of the composition.

The compositions of the invention contain various proportions of the two essential components thereof, the particular proportion being governed primarily by the use of the composition. Thus, while the weight ratio of the two components can vary, for example, from about 9:1 to 1:9, it is customary in surface coating applications to employ compositions containing a minor proportion of the 2-alkenyloxy compound. Excellent results have been obtained with compositions containing about 20% to 45% by weight of the 2-alkenyloxy compounds.

The compositions of the invention are cured to hard tough resinous material by application of heat in the presence of acidic curing agents. Among suitable curing agents are phosphoric acid, butyl dihydrogen phosphate, oxalic acid, p-toluene sulfonic acid and benzene disulfonic acid. Although various amounts of the acidic substances can be used to efiect cure, about an added 0.2% to 5% by weight of the composition is ordinarily employed. It has been found that phosphoric acid is particularly effective for curing the composition, especially when about an added 1% to 2% is used.

The compositions containing the acidic curing agent undergo cure by heating at about 250 F. to 450 F. The time needed for complete cure will vary inversely with the temperature' Thus, while 60 minutes time may be needed at 300 B, only minutes are required at 400 F.

solvent for the uncured composition.

The chemical reactions which occur during the curing are extremely complex and are not fully understood. The epoxide groups of the glycidyl polyether may couple with the hydroxyl groups also in the polyether,'with the hydroxyl groups of the 2-alkenyloxy compound and/or with the acid curing agent. The 2-alkenyl groups of the methylol-substituted benzene also appear to enter corresponding alkenyloxybenzene compounds.

In using the composition of the invention, various other substances can be incorporated therewith besides corporation of such materials as pigments, other resins, plasticizers, fillers and dyes.

While various auxiliary materials may be employed in combination as adjuvants with the composition, the use of these added substances is not indispensable.

1.0 in admixture with 0.2% to 3% of a polyvinyl acetal resin and at least one compound of the class consisting of 2-aikenyloxybenzenes having 1 to 3 methylol groups which are linked singly at the 2, 4 and 6 positions on the benzene rings.

The following examples are given for the purpose of illustrating several specific embodiments of the invention which are not to be construed as limited to particular details described therein. The parts are by weight.

Example 1 AOB in this and subsequent examples.

Compositions in solution of equal parts of Cellosolve acetate and toluene were prepared containing 75 parts of polyether B, 25 parts of AOB, 1.5 parts of phosphoric acid and the number of parts of polyvinyl butyral (Butvar B76) indicated in the tabulation below. The solutions were flowed out on plate glass panels and curing was effected by baking for 20 minutes at 375 F. The baked films were examined for crawling with the following results.

Parts of Polyvinyl Butyral Crawling x 0.5 Very slight. 1.0 None. 1.5 Do. 2.0 Do.

Example 2 The presence of the polyvinyl butyral does not adversely affect the caustic resistance of cured films. A solution was prepared containing 73.1 parts of polyether B, 24.4 parts of AOB, 1.5 parts of phosphoric acid and 1.0 part of polyvinyl butyral (Butvar B76) dissolved in 77.5 parts of Cellosolve acetate, 77.5 parts of methyl isobutyl ketone, 47.2 parts of methyl isobutyl carbinol, and 22.5 parts of n-butanol. The formulation was applied to a le-gauge cold rolled steel panel by dipping, six successive coatings being applied with curing by baking for minutes at 300 F. for the first five coats and curing for one hour at 350 F. for the last. The coated panel was then immersed for 16 hours in boiling 20% aqueous sodium hydroxide solution. Inspection of the cured film showed it to be unaifected by this treatment.

Example 3 A pigmented coating composition was prepared by grinding 23% by weight of chromium oxide pigment and 73% by weight of vehicle in solution of organic solvent,

- Gardner impact tester at 28 inch pounds impact, (2)

flexibility by bending 180 over a one-eighth inch mandrel, and (3) MEK resistance by contacting for 5 minutes with methyl ethyl ketone. The results are tabulated as follows with the key to the letter designations being given under the table.

Baking Baking Impact MEK l Temp, Time, Resist- Flexibility Resist- F. Min. ance auce 300 15 111.0 HLO so 300 U U SS 300 60 U U U 350 20 U U SS 350 40 U U U 350 U U U 400 10 U U U 400 20 U U U 400 30 U U U Key: HLO-Hairline cracks; SGSoft gel; SS-Slightly softened;

U Unaffected.

The glycidyl polyethers of polyhydric phenols referred to herein are condensates of polyhydric phenols with epichlorhydrin. Particularly when derived from dihydric phenols, these materials are known as ethoxyline resins. See Chemical Week, vol. 69, page 27, for September 8, 1951.

We claim as our invention:

1. A composition comprising a mixture of (1) glycidyl polyether of a polyhydric phenol having a 1,2-epoxy equivalency greater than 1.0, (2) a 2-alkenyloxybenzene containing 1 to 3 methylol groups linked singly at the 2, 4 and 6 positions on the benzene ring, and (3) about 0.2 to 3% of a polyvinyl acetal resin.

2. A composition comprising (1) glycidyl polyether of which are linked singly at the 2, 4 and 6 positions on the benzene ring, which mixture contains a major proportion of the 2-alkenyloxybenzene having 3 methylol groups linked to the benzene ring, and (3) about 0.2 to 3% of a polyvinyl acetal resin of an alkanal of 2 to 4 carbon atoms.

linked singly at the 2, 4 and 6 positions of the benzene ring, and (3) about 0.5 to 2% of polyvinyl butyral resin.

4. A composition as defined in claim 3 wherein the dihydric phenol is 2,2-bis(4-hydroxyphenyl)propane, and the molecular weight of the polyether is about 1200 to 4000.

5. A composition comprising (1) glycidyl polyether of of a dihydric phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 in uniform combination with (2) a mixture of allyloxybenzencs containing 1 to 3 methylol groups linked singly at the 2, 4 and 6 positions on the benzene ring, which mixture contains a major proportion of the allyloxybenzene having 3 methylol groups linked to the benzene ring, which composition contains about 20 to 45% by weight of said mixture, and (3) about 0.5 to 2% of polyvinyl butyral resin.

6. A composition as defined in claim 5 wherein the dihydric phenol is 2,2bis(4-hydroxyphenyl)propane, and the molecular weight of the polyether is about 1200 to 4000.

7. A composition comprising a mixture of (1) glycidyl V polyether of a polyhydric phenol having a 1,2-epoxy equivalency greater than 1.0, (2) a 2-alkenyloxybenzene containing 1 to 3 methylol groups linked singly at the 2, 4 and 6 positions on the benzene ring, (3) about 0.2 to 3% of a polyvinyl acetal resin, and (4) about 0.2 to 5% by weight of an acidic curing agent.

8. A composition comprising (1) glycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane having a 1,2-epoxy equivalency between 1.0 and 2.0 and a molecular weight of about 1200 to 4000 in uniform combination with (2) n a mixture of allyloxybenzenes containing 1 to 3 methylol groups linked singly at the 2, ring, which mixture contains a major proportion of the allyloxybenzene having 3 methylol groups linked to the benzene ring, and which composition contains about 20 to 45% by weight of said mixture, (3) about 0.5 to 2% of polyvinyl butyral resin, and (4) about 1 to 2% by weight of phosphoric acid.

4 and 6 positions on the 2,606,935 Martin Aug. 12, 1952 

1. A COMPOSITION COMPRISING A MIXTURE OF (1) GLYCIDYL POLYETHER OF A POLYHYDRIC PHENOL HAVING A 1,2-EPOXY EQUIVALENCY GREATER THAN 1.0, (2) A 2-ALKENYLOXYBENZENE CONTAINING 1 TO 3 METHYLOL GROUPS LINKED SINGLY AT THE 2, 4 AND 6 POSITION ON THE BENZENE RING, AND (3) ABOUT 0.2 TO 3% OF A POLYVINYL ACETAL RESIN. 